Process for the production of a catalyst suitable for the oxidation of methanol to formaldehyde

ABSTRACT

1. A PROCESS OF PREPARING A CATALYST SUITABLE FOR OXIDIZING METHANOL WITH AN OXYGEN CONTAINING GAS TO FORM FORMALDEHYDE, SAID CATALYST HAVING AN MOO3:FE2O3 WEIGHT RATIO OF BETWEEN 1:1 AND 10:1 COMPRISING COPRECIPITATING MOLYBDENUM AND IRON AS MOLYBDENUM OXIDE AND IRON OXIDE FROM AN AQUEOUS MIXTURE OF A MOLYBDENUM SALT CONTAINING MOLYBDENUM IN AN ORGANIC FORM AND AN IRON SALT WHICH IS WATER SOLUBLE FERROUS OR FERRIC SALT, MIXING TITANIUM DIOXIDE IN AN AMOUNT OF 1 TO 90 WEIGHT PERCENT OF THE TOTAL OXIDES WITH THE COPRECIPITATE AND TREATING THE MIXTURE AT 350 TO 600* C. IN AN OXIDIZING ATMOSPHERE.

um @kw H Ma, 8 7 54 5 2 xm Q man Mal754521 UITABLE FOR THE nUcTloN 0F A CATALYST s oF METHANOL 'ro FORMALDEHYDE Filed Aug. 51, 1972 H. FRIEDRICH ETAI- OXIDATION PRocEss FOR THE Pao United States Patent O "ice U.S. Cl. 252-469 24 Claims ABSTRACT OF THE DISCLOSURE Catalysts for the oxidation of methanol to formaldehyde Iare prepared having an MoOatFezOa weight ratio below :1 by coprecipitating d-issolved molybdenum and iron compound, mixing up to 90% of titanium dioxide with the coprecipitate, molding the mixture and finally calcining at elevated temperature.

The present invention is directed to a process for the production of a catalyst for ythe oxidation of methanol with oxygen containing gases, eg., air or oxygen, to formaldehyde in which there 'are u-sed oxide compounds of molybdenum land iron having a weight ratio of below 10:1. The invention also concerns the use of the catalyst to make formaldehyde from methanol.

Formaldehyde can `be produced by the ox-idation of methanol with air or oxygen in the presence of oxidic catalysts, especially those that contain molybdenum and 'iron oxides. Since the reaction 'is strongly exothermic in the industrial carrying out of the methanol oxidation, there lare used tube bundle re-actors from which the heat of reaction can be removed by `a `cooling medium. The catalyst-s are most commonly filled into the reaction tubes in the form of extrusions or tablets measuring between 2 -to 4 mm.

Because of a continual improvement in the catalyst the yields in this process are high, they are stated to be 90 to 94%. Besides the production of high yields there are further requirements on `the catalysts `in order that the process can be carried out in an industrially and economically satisfactory manner. Among these further requirements it is especially important that the shaped catalyst bodies have high mechanic-al strength; high spacetime-yield and low cost of the production.

The present invention is based `on lthe problem of developing a process for the production of `a catalyst for the oxidation of methanol with an oxygen-containing gas, preferably air, with a content of an oxidic combination of molybdenum and iron with an MoO3:Fe2O3 weight ratio below 10:1 and which can be much lower, eg., 3.921 and can be as low as 1:1, which c-atalyst is more abrasion resistant land more favorably priced than previous catalysts and which makes possible high space-timeyields lat simultaneously higher operating reliability.

According to this invention the problem is solved by intimately mixing the wet, dried or calcined precipitate obtained by coprecip'itation of dissolved molybdenum land iron compound with up to 90 weight percent, e.g., las low as 1 weight percent, preferably 3 to 60 weight percent, of titanium dioxide based on the water free coprecipitate, pasting the mixture with liquid 'and/ or mold assist agents, if necessary after renewed calc'ination, and working to molded objects and subsequently heating these objects stepwise 'in an oxidizing atmosphere, -for example, within Patented Oct. 22, 1974 24 hours, to a temperature between 350 land 600 ,C., preferably 400 to 500 C. and calcining at the final temperature for up to 24 hours. The heating between 350 and 600 C. can be for a time of 1 to 72 hour-s and the nal calcining can be for a time as short as 0.5 hours.

In one variant of the process of production the precipitate can be calcined at 350 to 600 C., preferably at 400 to 500 C. for up to 24 hours. The calcining can be for yas little as 0.5 hours. This calcining 'is before adding the titanium dioxide.

However, the mixture of dried or calcined precipitate and titanium -dioxide prior to the working into molded objects can be calcined for up to 24 hours at 350 to 600 C., preferably at 400 to 500 C. The calcining can be for as little `as 0.5 hour.

As previously pointed out especially good catalysts are obtained if the MoO3:Fe2O3 ratio in the catalysts are below 10:1 and the T'iO2 content is 3 to 60 weight percent. The lower limit on the lyioO3zfFe2O3y ratio can be that stated previously.

Other :advantageous properties are obtained with oatalystis according to the invention if there is provided a content of titanium dioxide up to 90 weight percent, based on the sum of the oxidic compounds of molybdenum and iron. Thus the weight ratio of MoO3:tFe2O3:TiO2 can be 9-6:14:90. To be sure such catalysts do not have the maximum activity -as a catalyst 'in the preparation of formaldehyde from methanol; their advantage is much more in the reduction in cost of the catalyst at practically unchanged, or often at even increased selectivity. The modification with higher amounts of titanium dioxide is rof special interest yif 'in a tirst step the main portion of the reactants are allowed to react with as high as possible selectivity using such catalysts and thereafter in a second step the still unreacted reaction gas is allowed to react on a catalyst with higher activity.

`Unless otherwise indicated all parts and percentages lare by weight.

Within the space of the process of production of the invention it has also ybeen found suitable to stepwise within 24 hours, heat fthe molded objects with the introduction of air to a temperature of 430 C. and iinally to calcine for 5 hours at this temperature.

The preparation of Ithe molded body can take place in the `following manner. The vmixture of the coprecipitate vand titanium dioxide can be pressed into tablets of about 3-4 mm. diameter and height in a tablet press with addition of a mold lubricant, eg., stearic acid. Another pressing procedure provides for pressing the mixture of the coprecipitate with titanium dioxide after forming a paste with -a liquid mold lubricant, eg., water, to form extrusions measuring 3 to 5 mm. by 3 to 5 mm.

If catalysts having an irregular particle shape lare preferred then a mixture of the coprecipitate with titanium dioxide after jaddition of -a liquid mold assist agent, eg., water, can be spread out on a support and after drying in air broken into particles of about 3-4 mm. diameter. The invention goes beyond the catalysts obtained by the described proces-s. This is characterized by a composition of oxidic compounds yof `molybdenum `and iron with a MoO3zFe2O3 weight ratio below 10:1 and a content of up to weight percent titanium dioxide, the lower limits being as indicated above.

Finally the invention is concerned with the use of the novel catalysts in processes for the oxidation of methanol with oxygen containing gases, especially air, to form formaldehyde. The reaction can be carried out at conventional temperatures and pressures for such reaction, eg., in a fixed bed reactor at a temperature of 240-450 C. and a mol percent of methanol in the methanol-air mixture of 6.0 to 7.5%.

A high mechanical strength in the molded catalyst is necessary in order that there does not occur an undesired progressive drop in the pressure in the reaction tubes during operation due to the breaking of the molded catalyst. With increasing drop in pressure there would occur a reduction in output as well as an increase in side reactions, so far as there is not provided a compensatory increase in the pressure of the methanol-air mixture iiowing in the reaction tubes. Because of the size of the required gas mixture this method of operation, however, is tied to a material increase in cost of operation. The mechanical strength of the catalyst therefore is of great significance as is also pointed out in German Pat. 1,144,252 and German Pat. 1,282,611.

The titanium dioxide content of the catalyst provided by the invention strongly increases the mechanical strength. While for example in German Pat. 1,144,252 there is stated an average breaking limit of 7.4 kg. per particle (extruded cylinders 3.5 x 3.5 mm.) for the molybdenum oxide-iron oxide catalyst described therein having a weight ratio of Mo:Fe of 3.9 to 4.3, the breaking limit of the molybdenum-iron-titanium oxide catalysts of the present invention prepared by the process of example 1 of the present case is up to 120% higher as can be seen from the following Table 1.

TABLE 1 Catalyst (extruded object) Since the cost of the catalysts and tube bundle reactors are high it is worth striving for a high space-time-yield (kg. formaldehyde per liter or kg. of catalystXhours). The space-time-yield is dependent upon the activity and selectivity of the catalyst and is limited by the effect of temperature. The titanium dioxide containing catalysts of the invention surprisingly have an especially high spacetirne-yield. It can, depending on the composition of the catalyst, amount to up to 2 kg. HCHO/liter or kg. of catalystxhour (the apparent density of the TiO2 containing catalysts in extruded articles of 3.5 3.5 mm. is about 1 kg./ liter). For molybdenum-iron oxide catalysts which do not contain titanium oxide according to German Pat. 1,144,252, German Pat. 1,282,611 and Germany offenlegungsschrift 1,667,270 there are obtained space-timeyields between 0.5 and 0.9 kg. HCHO/liter catalystX hour.

Besides a high space-time-yield low production costs are also desirable for a catalyst. With the usual molybdenum-iron oxide catalysts there are high raw material costs, especially due to the high molybdenum content. With the mixed molybdenum-iron titanium oxide catalysts of the invention the production costs are substantially lower because of the lower molybdenum contents. Thus the catalyst raw material costs are reduced about 25% by the addition of about 30 weight percent Ti02.

Besides the noted advantages possessed by the mixed catalysts of the invention there was found surprisingly the special advantage of a remarkably small dependence of the formaldehyde and carbon monoxide formation on temperature in the practical reaction region.

The strongly exothermic reaction of methanol with oxygen to form formaldehyde and water proceeds with the setting free of 1190 kilocalories per kg. of methanol. In an undesired side reaction a part of the methanol on the catalyst, however, reacts to form carbon monoxide and water, whereby per kg. of reacted methanol there arise 2850 kcal. At very high temperatures the methanol burns to carbon dioxide and water whereupon an additional 2100 kcal. per kg. of methanol are set free. If the side reaction to carbon monoxide takes place to too great an extent,

there occurs not only an undesired reduction in yield but also an increase in temperature in the catalyst which leads to an increase of the speed of reaction with further hastening of the side reaction and finally to complete burning of the methanol.

A good catalyst therefore should not only produce little carbon monoxide in the stationary working state but should also not be too dependent upon temperature' changes, especially on increases in temperature.

The temperature sensitivity of the catalyst for carrying out and regulating the reaction is of greater significance especially in tube reactors. If it is large, small uctuations in the methanol concentration in the gas, in the amount of gas, in the distribution of the added gas to the individual reaction tubes, in the amount of cooling agent or in the temperature of the cooling agent quickly lead to a local overheating, on occasion even to the run away of the reactor. This danger is the greater the reaction, the greater is the diameter of the catalyst tubes. An industrially regulatory treatment of the problem is made more diicult because a temperature probe cannot be placed in each catalyst tube, whose number in an industrial reactor amounts to several thousand.

The damping inuence of the titanium oxide content of the molybdenum-iron oxide catalyst of the invention on the temperature dependency of the formation of formaldehyde and carbon monoxide formation is seen from the curves set forth in the accompanying FIGS. l and 2 for the given amounts.

In FIGS. 1 and 2 there are set forth graphically the experimental results utilizing a tube reactor having an inner diameter of 15 mm. and a filled catalyst length of 50 cm. and provided with a cooling jacket. The operating conditions correspond to those in the subsequent examples. With exception of the temperature of the cooling medium the experiments were run under identical conditions. FIG. .1 shows the results which were obtained with a molybdenum-iron oxide catalyst without Ti02 addition (composition of example 4); FIG. 2 shows the results which were produced by a molybdenum-iron oxide catalyst with a TiOZ content of 30 weight percent (composition of example 8). In FIG. l, the highest formaldehyde yield (based on the methanol added) is at a cooling agent temperature of 265 C. (see the lower curve with the arrow to the left), in FIG. 2, the highest formaldehyde yield is at 288 C. (see the lower curve with the arrow to the left). The upper broken line curve with the arrow to the left in FIGS. 1 and 2 shows the total methanol reaction. The curve with the arrow to the right in FIGS. l and 2 shows the methanol reaction to carbon monoxide. On the abscissa of FIGS. 1 and 2 this is entered the cooling agent temperature.

It can be seen from FIG. 1 that with pure molybdenumiron oxide catalyst a markedly maximum formaldehyde formation is present and the latter falls off sharply with increasing temperature. After the maximum is exceeded there occurs very quickly and strongly the undesired formation of carbon monoxide which can -be read off especially plainly from the exponential increase in the CO curve. In contrast as can be seen from FIG. 2 the molybdenum-iron-titanium oxide catalyst shows a very broad maximum for formaldehyde formation and above all does not show a steep falling off at higher temperature. This is expressed in reverse in the curve of carbon monoxide formation which is at a lower level than with the molybdenum-iron oxides catalyst and shows a substantially lower increase with increasing temperature.

A temperature increase of 20 C. over the maximum formaldehyde formation brings about with the molybdenum-iron catalyst a reduction in yield of formaldehyde of 2.1% (absolute) and an increase in carbon monoxide formation of 2.4%. With titanium dioxide containing catalyst the corresponding numbers are 0.4% and 1.0%.

The production of the mixed catalysts used in the invention can take place in various ways, for example, by

mixing an iron salt solution, for example, an aqueous ferric chloride solution, with an aqueous ammonium heptamolybdate solution and repeatedly Washing the Mo- Fe-oxide precipitate, mixing the washed precipitate with the Ti2, filtering off the oxide mixture and drying the filter cake. The dried lter cake is homogenized with water and the paste obtained is pressed through a nozzle. The strands obtained is dried, broken and the molded bodies calcined.

In place of ferric chloride there can be used other water soluble iron salts such as ferric bromide, ferrous chloride, ferrie nitrate, ferric sulfate or ferrous sulfate. In place of ammonium heptamolybdate there can be used sodium or potassium heptamolybdate.

EXAMPLE I There were added to a warm solution of 0.617 kg. of ammonium heptamolybdate in 12.4 liters of water at 60 C. with strong stirring within 30 minutes a solution of 0.34 kg. of FeCl3-6H20 in 6.8 liters of water, whereas a precipitate of molybdenum-iron oxides formed. The precipitate was allowed to settle until about 10 liters of clear solution could be decanted off. The Mo/Fe oxide precipitated was then treated with 10 liters of water and suspended by stirring. After again allowing the mixture to settle, it was again decanted. In all, the resuspension and decanting off was carried out six times.

After the last decantation there was mixed With the Mo/Fe-oxide precipitate 0.215 kg. of Ti02. The Mo/Fe/ Ti-oxide mixture was separated off and finally dried for 2 days at 100 C. whereupon there were obtained 0.74 kg. of Mo/Fe/Ti-oxide crude catalyst.

The further working up of the Mo/Fe/Ti-oxide crude catalyst was accomplished by homogenizing with water in a mortar mill, whereupon there was produced a paste having a water content of about 45 weight percent. This product was divided in half with part (a) being pressed through a nozzle having a diameter of 4.7 mm. and part (b) lbeing pressed through a nozzle having a diameter of 4 mm.

The strands obtained were dried in air for 2 days and then broken into shaped bodies having an average length of (a) about 4.0 mm. and (b) about 3.3 mm., respectively. The shaped bodies were brought to a temperature of 430 C. within 24 hours while introducing air and held for 5 hours at this temperature. The finished mixed catalyst had a composition of 58.2 weight percent M003, 12.0 weight percent Fe203 and 29.8 weight percent Ti02, a specific surface area (BET) of 9.5 m.2/g. and shaped body measurements of cross section (a) 3.5 mm. diameter and 3.5 mm. length and (b) 2.95 mm. diameter and 3.0 mm. length.

The average breaking limit of the shaped bodies was for (a) 15 kg. and for (b) 9.9 kg.

For the production of mixed catalysts with a different Mo/Fe/Ti-oxide ratio the process described in example 1 was employed with only the amount of ammonium heptamolybdate or ferric chloride or Ti02 being varied.

EXAMPLE II There were poured into a fine steel tube having an inner diameter of 15 mm. 82 grams of the catalyst produced according to example 1(a), corresponding to a bed layer height of 49.9 cm.

A mixture of 4 moles of CH30H plus 57.5 moles of air at an entrance temperature of 250 C. Was led hourly through this reaction tube around which flowed oil at a temperature of 290 C.

The CHSOH conversion was 98.8% whereby 3.69 moles of HCHO/hour (92.3% of theory) were obtained with a yield of 1.35 kg./kg. catalyst X hour.

lEXAMPLE III There were poured into a fine steel tube having an inner diameter of 19 mm. 133.3 grams of the catalyst produced according to example 1(b) [bed layer height 47.8 cm.]

There were led hourly through this reaction tube a mixture of 3.70 moles of CHSOH plus 50.7 moles of air at an entrance temperature of 255 C. The oil bath around the reaction tube had a temperature of 290 C.

The CHBOH transformation was 99.35%; thereby there were obtained 3.44 moles of HCHO/h. (93.0% of theory), HCHO- yield 0.775 kg./kg. catalyst hour.

EXAMPLE IV 72 grams of a comparison catalyst produced according to example 1 but without the addition of Ti02 and in the form of shaped bodies of about 3.5 x 3.5 mm. were lled into the reaction tube having an inner diameter of 15 mm. (bed layer height 47.2 cm.). The catalyst had a composition of 80.7 weight percent M003 plus 19.3 Weight percent Fe203. There were led over the catalyst hourly at an oil bath temperature of 270 1C. a mixture of 2 moles of CH30H plus 28.65 moles of air at an entrance temperature of 240 C. Thereby 99.6% of the CHSOH was transformed and there were obtained 1.82 moles of HCHO/h. (91.4% of theory). HCHO- yield 0.76 kg./kg. catalyst hour.

EXAMPLE V There were poured into the reaction tube having an inner diameter of 15 mm. 49 grams (bed layer height 35.2 cm.) of a catalyst produced according to example I having the composition 40.8 Weight percent M003 plus 9.0 Weight percent Fe203 plus 50.2 Weight percent TiOz. The catalyst shaped bodies measured 4.2 X 4.2 mm. (i.e., they were cylinders having a diameter of 4.2 cm. and a height of 4.2 mm.).

At an oil bath temperature of 320 C. there were introduced hourly into the reaction tube a mixture heated to 270 C. of 2.51 moles of CHEOH plus 35.7 moles of air, whereupon the CH30H transformation was 97.1%. There was obtained 2.28 moles of HCHO/h. (90.0% of theory). HCHO yield 1.4 kg./kg. catalystXhour.

EXAMPLE VI 121.7 grams of the catalyst of example V were poured into the 19 mm. reaction tube (height of the bed layer 49.6 cm.) which was surrounded by 300 C. hot oil. There were led through hourly a mixture of 3.84 moles of CHBOH plus 55.7 moles of air which had an entrance temperature of 245 C.

At a CHaOH conversion of 98.7% there were obtained 3.52 moles of HCHO/h. (91.8% of theory). HCHO- yield 0.87 kg./kg. catalyst hour.

EXAMPLE VII There were poured into the reaction tube having an inner diameter of 15 mm. 88 grams (bed layer height 46.5 cm.) of catalyst produced according to example I and having the composition 67.6 weight percent M003 plus 13.6 weight percent Fe203 plus 18.8 weight percent Ti02. The catalyst shaped bodies measured 3.1 x 3.1 mm.

At an oil bath temperature of 290 C., were led hourly over the catalyst bed a mixture of 2.25 rnoles of CH30H plus 31.9 moles of air heated to an entrance temperature of 245 C. The CH30H conversion was 99.1%, the HCHO yield 2.08 moles/h. (92.4% of theory). HCHO- yie'l'd 0.71 kg./kg. catalystXhour.

EXAMPLE VIII A Mo/Fe-oxide precipitate obtained by precipitating and washing as in example I was separated olf, dried at 100 C. for 24 hours and then calcined for 5 hours at 430 C. The 0.52 kg. of obtained Mo/Fe-oxide together with 0.224 kg. of Ti02 were worked up with Water to` a homogenous paste in a mortar mill, which paste was stretched out to 4 mm. thick on a support. After air drying for about 24 hours the pieces obtained were reduced to a particle size of 2.8-4.0 mm. and calcined as described in example 1. Composition of the catalyst: 56.5 weight percent M003 plus 13.4 weight percent F6203 plus 30.1 weight percent TiOz.

75 grams (height of the bed layer 44.8 cm.) of this catalyst were poured into the reaction tube having a l mm. inner diameter. The catalyst consisted of particles of the 2.8-4 mm. fraction.

At an oil bath temperature of 300 C., there were led over the catalyst layer hourly a mixture of 5.5 moles of CHSOH plus 71.0 moles of air heated to 260 C. The CH3OH conversion was 98.1%. There was obtained 5.06 mois/h. of HCHO (92.1% of theory). HCHO- yield 2.02 kg./kg. catalystxhour.

EXAMPLE IX There were placed in the reaction tube having an inner diameter of 15 mm. 80 grams (bed layer height 49 om.) of the catalyst of example VIII. This catalyst was thermally pretreated for the following experiment for 2 hours at 500 C.

At an oil bath temperature of 310 C., there were led through the reaction tube a mixture of 2.21 moles of CH3OH. Conversion was 99.1% and the HCHO yield was 2.07 moles/h. (93.5% of theory). HCHO- yield 0.775 kg/kg. catalystXhour.

EXAMPLE X The reaction tube having an inner diameter of 15 mm. was lled with 79 grams (bed layer height 50.1 cm.) of a catalyst produced according to example 1 and having the composition 78.2 Weight percent M003 plus 18.8 weight percent Fe203 plus 3.0 weight percent TiOg. The shaped Ibodies of the catalyst measured 3.1 x 3.1 mm.

There were hourly passed through the reaction tube which was surrounded by circulating oil at 275 C. a mixture of 2.15 moles of CH3OH plus 32.1 moles of air heated to 245 C. The CHaOH was converted to an extent of 99.2%. There were obtained 1.98 moles/h. (92.1% of theory) of formaldehyde which corresponded to a HCHO- yield of 0.75 kg./kg. catalystxhour.

EXAMPLE XI A crude Mo/Fe/Ti-oxide catalyst obtained according to example I was ldried for 2 days at 100 C. and calcined for 5 hours at 430 C. The calcined crude catalyst was treated with 3 weight percent of stearic acid as a mold lubricant by means of a roller block and then pressed to tablets of about 4 x 4 mm. (i.e., diameter 4 m., height 4 mm.). The tablets were brought to a temperature of 430 C., Within 24 hours while introducing air and then calcined at this temperature for 5 hours. The composition of the catalyst was 57.2% M003 plus 12.1% Fe203 plus 30.7% Ti02.

There were poured into the reaction tube having an inner diameter of 15 mm. 76 grams (height of the bed layer 48 cm.) of this catalyst.

At an oil bath temperature of 290 C., there were led hourly through the catalyst bed a mixture of 2.01 moles CH3OH plus 28.7 moles of air heated to 250 C. The CHaOH conversion was 99.3% and the HCHO yield was 1.85 moles/h. (92.0% of theory). HCHO= yield 0.73 kg./kg. catalystXhour.

What is claimed is:

1. A process of preparing a catalyst suitable for oxidizing methanol with an oxygen containing gas to form formaldehyde, said catalyst having an M003:Fe203 weight ratio of between 1:1 and 10:1 comprising coprecipitating molybdenum and iron as molybdenum oxide and iron oxide from an aqueous mixture of a molybdenum salt containing molybdenum in an anionic form and an iron salt which is a water soluble ferrous or ferr-ic salt, mixing titanium dioxide in an amount of 1 to 90 weight percent of the total oxides with the coprecipitate and treating the mixture at 350 to 600 C. in an oxidizing atmosphere.

2. A process according to Claim 1 wherein the titanium dioxide is 3 to 60 weight percent of the total oxides.

3. A process according to Claim l wherein the coprecipitate is wet mixed with the titanium dioxide.

4. A process according to `Claim 1 wherein the coprecipitate is dried prior to mixing With the titanium dioxide.

5. A process according to Claim 1 wherein the coprecipitate is calcined prior to mixing with the titanium dioxide.

6. A process according to Claim 1 including the step of shaping the titanium dioxide containing oxide mixture.

7. A process according to Claim 1 wherein the molybdenum salt is ammonium heptamolybdate, potassium heptamolybdate or sodium heptamolybdate.

8. A process according to Claim 7 wherein the iron salt is a ferric salt.

9. A process according to Claim 7 wherein the molybdenum salt is ammonium heptamolybdate.

10. A process according to Claim 1 wherein the treatment of the mixture in the oxidizing atmosphere is carried out stepwise for a time of up to 24 hours to a temperature ranging from 350 to 600 C. and is followed by calcining at the final temperature in said range for up to 72 hours.

11. A process according to Claim 10 wherein the treatment in the oxidizing atmosphere is at 400 to 500 C.

12. A process according to Claim 10 wherein the coprecipitate is calcined at 350 to 600 C. for up to 24 hours before adding the T iOZ.

13. A process according to Claim 12 wherein the coprecipitate is calcined at 400 to 500 C.

14. A process according to Claim 10 wherein the titanium dioxide containing oxide mixture is made into a pasty mixture with the aid of a liquid mold assist agent and worked into shaped bodies.

1S. A process according to Claim 10 wherein the coprecipitate in dried or calcined form is mixed with titanium dioxide and is calcined for up to 24 hours at 350- 600 C. and then worked into shaped ibodies.

16. A process according to Claim 1S in which the calcining prior to shaping is at 400-500 C.

17. A process according to Claim 10 wherein the mixture of oxides of molybdenum and iron has 3-60 weight percent of Ti02 added thereto so that the residual amount of M003 plus Fe2'03 is 97-40 weight percent of the mixture.

18. A process according to Claim 10 wherein the weight ratio of Mo03:Fe203:Ti02 is 9-6:14:90.

19. A process according to Claim 10 wherein the calcining is at 430 C. for 5 hours.

20. A process according to IClaim 10 wherein the mixture of coprecipitate and titanium dioxide is pressed into tablets having a diameter of about 3-4 mm. and a height of about 3-4 mm. with the aid of a mold lubricant.

21. A process according to Claim 10 wherein the mixture of coprecipitate and titanium dioxide is formed into a paste with a liquid mold assist agent and pressed into strands measuring 3.5 x 3.5 mm.

22. A process according to Claim 10 wherein the mixture of coprecipitate and titanium dioxide is mixed with a liquid mold assist agent and spread out on a support, dried in air and then broken .into Particles having a diameter of about 3-4 mm.

9 l0 23. A catalyst prepared according to Claim 1. FOREIGN PATENTS 24. A catalyst according to Claim 23 having 3 to 60 A weight percent titaniuln dioxide based on the total of 2306 1914 Great Bntam 252,470 M003 P1us F6203 P1S T102- DANIEL E. WYMAN, Primary Examiner References Cited 5 W. I. SHINE, Assistant Examiner UNITED STATES PATENTS U.S.Cl.X.R.

3,152,997 10/1964 Natta et al. 252-470 252-470; 260-603 R 

1. A PROCESS OF PREPARING A CATALYST SUITABLE FOR OXIDIZING METHANOL WITH AN OXYGEN CONTAINING GAS TO FORM FORMALDEHYDE, SAID CATALYST HAVING AN MOO3:FE2O3 WEIGHT RATIO OF BETWEEN 1:1 AND 10:1 COMPRISING COPRECIPITATING MOLYBDENUM AND IRON AS MOLYBDENUM OXIDE AND IRON OXIDE FROM AN AQUEOUS MIXTURE OF A MOLYBDENUM SALT CONTAINING MOLYBDENUM IN AN ORGANIC FORM AND AN IRON SALT WHICH IS WATER SOLUBLE FERROUS OR FERRIC SALT, MIXING TITANIUM DIOXIDE IN AN AMOUNT OF 1 TO 90 WEIGHT PERCENT OF THE TOTAL OXIDES WITH THE COPRECIPITATE AND TREATING THE MIXTURE AT 350 TO 600* C. IN AN OXIDIZING ATMOSPHERE. 